Reactor continuity

ABSTRACT

A supported catalyst system comprising a phosphinimine ligand containing catalyst on a porous inorganic support treated with a metal salt has improved reactor continuity in a dispersed phase reaction in terms of initial activation and subsequent deactivation. The resulting catalyst has a lower consumption of ethylene during initiation and a lower rate of deactivation. Preferably the catalyst is used with an antistatic agent.

FIELD OF THE INVENTION

The present invention relates to improving the continuity of a catalystcomprising a phosphinimine ligand and a hetero atom ligand, preferablybulky, and the reaction thereof in a dispersed phase (i.e. gas phase,fluidized bed or stirred bed or slurry phase) olefin polymerization.There are a number of factors which impact on reactor continuity in adispersed phase polymerization. A decrease in catalyst productivity oractivity is reflected by a decrease in ethylene uptake over time but mayalso result in a lower kinetic profile and potentially a lower potentialfor fouling.

BACKGROUND OF THE INVENTION

Single site catalysts for the polymerization of alpha olefins wereintroduced in the mid 1980's. These catalysts are more active than theprior Ziegler Natta catalysts, which may lead to issues of polymeragglomeration. Additionally, static may contribute to the problem. As aresult reactor continuity (e.g. fouling and also catalyst life time) maybe a problem.

The kinetic profile of many single site catalysts starts off with a veryhigh activity over a relatively short period of time, typically aboutthe first five minutes of the reaction, the profile then goes through aninflection point and decreases rapidly for about the next five minutesand thereafter there is period of relative slower decline in the kineticprofile. This may be measured by the ethylene uptake, typically instandard liters of ethylene per minute in the reactor.

U.S. Pat. No. 6,147,172 issued Nov. 14, 2000 to Brown et al. assigned toNOVA Chemicals International S.A. discloses a catalyst comprising aphosphinimine ligand and a boron heterocyclic ligand, typically bulky.The patent teaches the catalyst may be supported (Col. 21, part C) butdoes not suggest any treatment of the support as set out in the presentdisclosure.

Canadian Patent Application 2,716,772 filed Oct. 6, 2010 discloses aprocess to improve the dispersed phase reactor continuity of catalysthaving a phosphinimine ligand by supporting the catalyst on a silicasupport treated with Zr(SO₄)₂₋₄H₂O. The support is also treated withMAO. This patent application fails to disclose or suggest the type ofcatalyst of the present disclosure.

U.S. Pat. No. 6,734,266 issued May 11, 2004 to Gao et al., assigned toNOVA Chemicals (International) S.A. teaches sulfating the surface ofporous inorganic support with an acid, amide or simple salt such as analkali or alkaline earth metal sulphate. The resulting treated supportmay be calcined. Aluminoxane and a single site catalyst are subsequentlydeposited on the support. The resulting catalyst shows improvedactivity. However, the patent fails to teach or suggest depositingzirconium sulphate on a metal oxide support.

U.S. Pat. No. 7,001,962 issued Feb. 21, 2006 to Gao et al., assigned toNOVA Chemicals (International) S.A. teaches treating a porous inorganicsupport with a zirconium compound including zirconium sulphate and anacid such as a fluorophosphoric acid, sulphonic acid, phosphoric acidand sulphuric acid. The support is dried and may be heated under air at200° C. and under nitrogen up to 600° C. Subsequently, a trialkylaluminum compound (e.g. triethyl aluminum) or an alkoxy aluminum alkylcompound (e.g. diethyl aluminum ethoxide) and a single site catalyst aredeposited on the support. The specification teaches away from usingaluminoxane compounds. The activity of these supports is typically lowerthan the activity of the catalyst of U.S. Pat. No. 6,734,266 (compareTable 5 of U.S. Pat. No. 7,001,962 with Table 2 of U.S. Pat. No.6,734,266). The present invention eliminates the required acid reagentthat reacts with the zirconium compound.

U.S. Pat. No. 7,273,912 issued Sep. 25, 2007 to Jacobsen et al.,assigned to Innovene Europe Limited, teaches a catalyst which issupported on a porous inorganic support which has been treated with asulphate such as ammonium sulphate or an iron, copper, zinc, nickel orcobalt sulphate. The support may be calcined in an inert atmosphere at200 to 850° C. The support is then activated with an ionic activator andthen contacted with a single site catalyst. The patent fails to teachaluminoxane compounds and zirconium sulphate.

U.S. Pat. No. 7,005,400 issued Feb. 28, 2006 to Takahashi assigned toPolychem Corporation teaches a combined activator support comprising ametal oxide support and a surface coating of a group 2, 3, 4, 13 and 14oxide or hydroxide different from the carrier. The support is intendedto activate the carrier without the conventional “activators”. However,in the examples the supported catalyst is used in combination withtriethyl aluminum. The triethyl aluminum does not appear to be depositedon the support. Additionally, the patent does not teach phosphiniminecatalysts.

U.S. Pat. No. 7,442,750 issued Oct. 28, 2008 to Jacobsen et al.,assigned to Innovene Europe Limited teaches treating an inorganic metaloxide support typically with a transition metal salt, preferably asulphate, of iron, copper, cobalt, nickel, and zinc. Then a single sitecatalyst, preferably a constrained geometry single site catalyst and anactivator are deposited on the support. The activator is preferably aborate but may be an aluminoxane compound. The disclosure appears to bedirected at reducing static in the reactor bed and product in theabsence of a conventional antistatic agent such as STADIS®.

U.S. Pat. No. 6,653,416 issued Nov. 25, 2003 to McDaniel at al.,assigned to Phillips Petroleum Company, discloses a fluoridesilica—zirconia or titania porous support for a metallocene catalystactivated with an aluminum compound selected from the group consistingof alkyl aluminums, alkyl aluminum halides and alkyl aluminum alkoxides.Comparative examples 10 and 11 show the penetration of zirconium intosilica to form a silica-zirconia support. However, the examples(Table 1) show the resulting catalyst has a lower activity than thosewhen the supports were treated with fluoride.

None of the above art suggests treating the support with an antistaticagent.

The use of a salt of a carboxylic acids, especially aluminum stearate,as an antifouling additive to olefin polymerization catalystcompositions is disclosed in U.S. Pat. Nos. 6,271,325 (McConville etal., to Univation) and 6,281,306 (Oskam et al., to Univation).

The preparation of supported catalysts using an amine antistatic agent,such as the fatty amine sold under the trademark KEMANINE® AS-990, isdisclosed in U.S. Pat. Nos. 6,140,432 (Agapiou et al.; to Exxon) and6,117,955 (Agapiou et al.; to Exxon).

Antistatic agents are commonly added to aviation fuels to prevent thebuildup of static charges when the fuels are pumped at high flow rates.The use of these antistatic agents in olefin polymerizations is alsoknown. For example, an aviation fuel antistatic agent sold under thetrademark STADIS composition (which contains a “polysulfone” copolymer,a polymeric polyamine and an oil soluble sulfonic acid) was originallydisclosed for use as an antistatic agent in olefin polymerizations inU.S. Pat. No. 4,182,810 (Wilcox, to Phillips Petroleum). The examples ofthe Wilcox '810 patent illustrate the addition of the “polysulfone”antistatic agent to the isobutane diluent in a commercial slurrypolymerization process. This is somewhat different from the teachings ofthe earlier referenced patents—in the sense that the carboxylic acidsalts or amine antistatics of the other patents were added to thecatalyst, instead of being added to a process stream.

The use of “polysulfone” antistatic composition in olefinpolymerizations is also subsequently disclosed in:

1) chromium catalyzed gas phase olefin polymerizations, in U.S. Pat. No.6,639,028 (Heslop et al.; assigned to BP Chemicals Ltd.);

2) Ziegler Natta catalyzed gas phase olefin polymerizations, in U.S.Pat. No. 6,646,074 (Herzog et al.; assigned to BP Chemicals Ltd.); and

3) metallocene catalyzed olefin polymerizations, in U.S. Pat. No.6,562,924 (Benazouzz et al.; assigned to BP Chemicals Ltd.).

The Benazouzz et al. patent does teach the addition of STADIS antistaticagent to the polymerization catalyst in small amounts (about 150 ppm byweight). However, in each of the Heslop et al. '028, Herzog et al. '074and Benazouzz et al. '924 patents listed above, it is expressly taughtthat it is preferred to add the STADIS antistatic directly to thepolymerization zone (i.e. as opposed to being an admixture with thecatalyst).

None of the above art discusses the kinetic profile of the catalystsystem. One of the difficulties with high activity (“hot”) catalyst isthat they tend to have a very high initial reactivity (ethyleneconsumption) that goes through an inflection point and rapidly decreasesover about the first 10 minutes of reaction and then decreases at a muchlower rate over the next 50 minutes together with fluctuations inreactor temperature. It is desirable to have a high activity catalyst(e.g. more than about 1,300 grams of polymer per gram of supportedcatalyst normalized to 200 psig (1,379 kPa) ethylene partial pressureand 90° C. in the presence of 1-hexene comonomer) having a kineticprofile for a plot of ethylene consumption in standard liters ofethylene per minute against time in minutes, corrected for the volume ofethylene in the reactor prior to the commencement of the reaction, in a2 liter reactor over a period of time from 0 to 60 minutes is such thatthe ratio of the maximum peak height over the first 10 minutes to theaverage ethylene consumption from 10 to 60 minutes taken at not lessthan 40, preferably greater than 60 most preferably from 120 to 300 datapoints, is less than 7, preferably less than 6, most preferably lessthan 5.5.

The present invention seeks to provide a catalyst having a kineticprofile as described above, optionally having reduced static and its usein the dispersed phase polymerization of olefins.

SUMMARY OF THE INVENTION

In one embodiment the present invention provides a catalyst systemhaving an activity greater than 1,300 g of polymer per gram of supportedcatalyst per hour normalized to 1,379 kPag (200 psig) of ethylenepartial pressure and a temperature of 90° C. in the presence of 1-hexenecomonomer and a kinetic profile for a plot of ethylene consumption instandard liters of ethylene per minute against time in minutes, at areaction pressure of 1,379 kPag (200 psig) and 90° C., corrected for thevolume of ethylene in the reactor prior to the commencement of thereaction, in a 2 liter reactor over a period of time from 0 to 60minutes is such that the ratio of the maximum peak height over the first10 minutes to the average ethylene consumption from 10 to 60 minutestaken at not less than 40 data points, is less than 6, comprising:

(i) a porous inorganic oxide support having an average particle sizefrom 10 to 150 microns, a surface area greater than 100 m²/g, and a porevolume greater than 0.3 ml/g impregnated with

(ii) at least a 1 weight % based on the weight of said inorganic oxidesupport of Zr(SO₄)₂₋₄H₂O;

(iii) from 10 to 60 weight % of an aluminum activator based on theweight of said inorganic oxide support of said activator having theformula:

R¹² ₂AlO(R¹²AlO)_(q)AlR¹² ₂

wherein each R¹² is independently selected from the group consisting ofC₁₋₂₀ hydrocarbyl radicals and q is from 3 to 50; and

(iv) from 0.1 to 30 weight % of a catalyst of the formula:

wherein M is a group 4 metal having an atomic weight less than 179; Plis a phosphinimine ligand of the formula

wherein each R²¹ is independently selected from the group consisting ofa hydrogen atom; a halogen atom; C₁₋₁₀ hydrocarbyl radicals which areunsubstituted by or further substituted by a halogen atom; H is aheteroligand characterized by (a) containing a heteroatom selected fromN, S, B, O, P or Si, and (b) being bonded to M through a sigma or pibond with the proviso that H is not a phosphinimine ligand as definedabove or a ketamide ligand as defined below; L is an activatable ligand;n is 1, 2 or 3 depending upon the valence of M with the proviso that Lis not a cyclopentadienyl, indenyl or fluorenyl ligand.

In a further embodiment the present invention provides the abovecatalyst further comprising from 50 to 250 ppm based on the weight ofthe supported catalyst of an antistatic comprising:

(i) from 3 to 48 parts by weight of one or more polysulfones comprising:

-   -   (a) 50 mole % of sulphur dioxide;    -   (b) 40 to 50 mole % of a C₆₋₂₀ an alpha olefin; and    -   (c) from 0 to 10 mole % of a compound of the formula ACH═CHB

where A is selected from the group consisting of a carboxyl radical anda C₁₋₁₅ carboxy alkyl radical and B is a hydrogen atom or a carboxylradical provided if A and B are carboxyl radicals A and B may form ananhydride;

(ii) from 3 to 48 parts by weight of one or more polymeric polyamides ofthe formula:

R²⁰N[(CH₂CHOHCH₂NR²¹)_(a)—(CH₂CHOHCH₂NR²¹—R²²—NH)_(b)—(CH₂CHOHCH₂NR²³)_(c)H_(x)]H_(2-x)

wherein R²¹ is an aliphatic hydrocarbyl group of 8 to 24 carbon atoms;R²² is an alkylene group of 2 to 6 carbon atoms; R²³ is the groupR²²—HNR²¹; R²⁰ is R²¹ or an N-aliphatic hydrocarbyl alkylene grouphaving the formula R²¹NHR²²; a, b and c are integers from 0 to 20 and xis 1 or 2; with the proviso that when R²⁰ is R²¹ then a is greater than2 and b=c=0, and when R²⁰ is R²¹NHR²² then a is 0 and the sum of b+c isan integer from 2 to 20; and

(iii) from 3 to 48 parts by weight of C₁₀₋₂₀ alkyl or arylalkylsulphonic acid.

In a further embodiment the present invention provides a process ofmaking a catalyst system having an activity greater than 1,300 g ofpolymer per gram of supported catalyst per hour normalized to 1,379 kPag(200 psig) of ethylene partial pressure and a temperature of 90° C. inthe presence of 1-hexene comonomer and a kinetic profile for a plot ofethylene consumption in standard liters of ethylene per minute againsttime in minutes, at a reaction pressure of 1,379 kPag (200 psig) and 90°C., corrected for the volume of ethylene in the reactor prior to thecommencement of the reaction, in a 2 liter reactor over a period of timefrom 0 to 60 minutes is such that the ratio of the maximum peak heightover the first 10 minutes to the average ethylene consumption from 10 to60 minutes taken at not less than 40 data points, is less than 6.0,comprising:

(i) impregnating a porous inorganic support having an average particlesize from 10 to 150 microns, a surface area greater than 100 m²/g, and apore volume greater than 0.3 ml/g with

(ii) at least a 1 weight % aqueous solution of Zr(SO₄)₂₋₄H₂O, to providenot less than 1 weight % based on the weight of the support of saidsalt;

(iii) recovering the impregnated support;

(iv) calcining said impregnated support in one or more steps at atemperature from 300° C. to 600° C. for a time from 2 to 20 hours in aninert atmosphere;

(v) and either

-   -   (a) contacting said calcined support with a hydrocarbyl solution        of an aluminum activator compound of the formula: R¹²        ₂AlO(R¹²AlO)_(q)AlR¹² ₂ wherein each R¹² is independently        selected from the group consisting of C₁₋₂₀ hydrocarbyl radicals        and q is from 3 to 50 to provide from 10 to 60 weight % of said        aluminum compound based on the weight of said calcined support;        optionally, separating said activated support from said        hydrocarbyl solution and contacting said activated support with        a hydrocarbyl solution containing a single site catalyst as set        out below to provide from 0.1 to 30 wt % of said single site        catalyst; or    -   (b) contacting said support with a hydrocarbyl solution        containing an aluminum activator compound of the formula:

R¹² ₂AlO(R¹²AlO)_(q)AlR¹² ₂

-   -    wherein each R¹² is independently selected from the group        consisting of C₁₋₂₀ hydrocarbyl radicals and q is from 3 to 50        and a catalyst of the formula:

-   -    wherein M is a group 4 metal having an atomic weight less than        179; Pl is a phosphinimine ligand of the formula:

-   -    wherein each R²¹ is independently selected from the group        consisting of a hydrogen atom; a halogen atom; C₁₋₁₀ hydrocarbyl        radicals which are unsubstituted by or further substituted by a        halogen atom; H is a heteroligand characterized by (a)        containing a heteroatom selected from N, S, B, O or P; and (b)        being bonded to M through a sigma or pi bond with the proviso        that H is not a phosphinimine ligand as defined above or a        ketamide ligand as defined below; L is an activatable ligand; n        is 1, 2 or 3 depending upon the valence of M with the proviso        that L is not a cyclopentadienyl, indenyl or fluorenyl ligand to        provide from 10 to 60 weight % of said aluminum compound based        on the weight of said calcined support and form 0.1 to 30 wt %        of said singles site catalyst based on the weight of said        support; and

(vi) recovering and drying the catalyst.

In a further embodiment the present invention provides the above processfurther comprising contacting said catalyst with from 15,000 to 120,000ppm based on the weight of the supported catalyst of an antistaticcomprising:

(i) from 3 to 48 parts by weight of one or more polysulfones comprising:

-   -   (a) 50 mole % of sulphur dioxide;    -   (b) 40 to 50 mole % of a C₆₋₂₀ an alpha olefin; and    -   (c) from 0 to 10 mole % of a compound of the formula ACH═CHB        where A is selected from the group consisting of a carboxyl        radical and a C₁₋₁₅, carboxy alkyl radical; and B is a hydrogen        atom or a carboxyl radical provided if A and B are carboxyl        radicals A and B may form an anhydride;

(ii) from 3 to 48 parts by weight of one or more polymeric polyamides ofthe formula:

RN[(CH₂CHOHCH₂NR¹)_(a)—(CH₂CHOHCH₂NR¹—R²—NH)_(b)—(CH₂CHOHCH₂NR³)_(c)H_(x)]H_(2-x)

wherein R¹ is an aliphatic hydrocarbyl group of 8 to 24 carbon atoms; R²is an alkylene group of 2 to 6 carbon atoms; R³ is the group-R²—HNR¹; Ris R¹ or an N-aliphatic hydrocarbyl alkylene group having the formulaR¹NHR²; a, b and c are integers from 0 to 20 and x is 1 or 2; with theproviso that when R is R¹ then a is greater than 2 and b=c=0, and when Ris R¹NHR² then a is 0 and the sum of b+c is an integer from 2 to 20; and

(iii) from 3 to 48 parts by weight of C₁₀₋₂₀ alkyl or arylalkylsulphonic acid and optionally from 0 to 150 parts by weight of a solventor diluent.

In a further embodiment the present invention provides a dispersed phaseolefin polymerization process having improved reactor continuityconducted in the presence of the above catalyst further comprising anantistatic agent.

In a further embodiment the present invention provides a disperse phasepolymerization process comprising contacting one or more C₂₋₈ alphaolefins with a catalyst system which does not contain an antistaticagent, and feeding to the reactor from 10 to 80 ppm based on the weightof the polymer produced of an antistatic comprising:

(i) from 3 to 48 parts by weight of one or more polysulfones comprising:

-   -   (a) 50 mole % of sulphur dioxide;    -   (b) 40 to 50 mole % of a C₆₋₂₀ an alpha olefin; and    -   (c) from 0 to 10 mole % of a compound of the formula ACH═CHB        where A is selected from the group consisting of a carboxyl        radical and a C₁₋₁₅ carboxy alkyl radical and B is a hydrogen        atom or a carboxyl radical provided if A and B are carboxyl        radicals A and B may form an anhydride;

(ii) from 3 to 48 parts by weight of one or more polymeric polyamides ofthe formula:

R²⁰N[(CH₂CHOHCH₂NR²¹)_(a)—(CH₂CHOHCH₂NR²¹—R²²—NH)_(b)—(CH₂CHOHCH₂NR²³)_(c)H_(x)]H_(2-x)

wherein R²¹ is an aliphatic hydrocarbyl group of 8 to 24 carbon atoms;R²² is an alkylene group of 2 to 6 carbon atoms; R²³ is the groupR²²—HNR²¹; R²⁰ is R²¹ or an N-aliphatic hydrocarbyl alkylene grouphaving the formula R²¹NHR²²; a, b and c are integers from 0 to 20 and xis 1 or 2; with the proviso that when R²⁰ is R²¹ then a is greater than2 and b=c=0, and when R²⁰ is R²¹NHR²² then a is 0 and the sum of b+c isan integer from 2 to 20; and

(iii) from 3 to 48 parts by weight of C₁₀₋₂₀ alkyl or arylalkylsulphonic acid.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is the kinetic profile of the catalysts run in example 1.

DETAILED DESCRIPTION

As used in this specification dispersed phase polymerization means apolymerization in which the polymer is dispersed in a fluidpolymerization medium. The fluid may be liquid in which case thepolymerization would be a slurry phase polymerization or the fluid couldbe gaseous in which case the polymerization would be a gas phasepolymerization, either fluidized bed or stirred bed.

As used in this specification kinetic profile means a plot of ethyleneconsumption in standard liters of ethylene per minute against time inminutes, corrected for the volume of ethylene in the reactor prior tothe commencement of the reaction, in a 2 liter reactor over a period oftime from 0 to 60 minutes.

As used in this specification gram of supported catalyst means a gram ofthe catalyst system and activator on the support treated withZr(SO₄)₂.4H₂O.

As used in this specification ketamide ligand means a ligand of theformula:

wherein Sub 1 and Sub 2 are independently selected from the groupconsisting of C₁₋₂₀ hydrocarbyl radicals which are unsubstituted or maybe substituted by up to 4 hetero atoms selected from the groupconsisting of N, O, and S or up to three C₁₋₉ straight chain, branched,cyclic or aromatic radicals which may be unsubstituted or substituted bya C₁₋₆ alkyl radical or Sub 1 and Sub 2 taken together may form asaturated or unsaturated ring which may be substituted by up to 4 heteroatoms selected from the group consisting of N, O, and S and which ringmay be further substituted by up to three C₁₋₉ straight chain, branched,cyclic or aromatic radicals which may be unsubstituted or substituted byone or more C₁₋₆ alkyl radicals.

The Support

The support for the catalysts of the present invention is an inorganicoxide, preferably silica oxide, having a pendant reactive moiety. Thereactive moiety may be a siloxyl radical but more typically is ahydroxyl radical. The support should have an average particle size fromabout 10 to 150 microns, preferably from about 20 to 100 microns. Thesupport should have a large surface area typically greater than about100 m²/g, preferably greater than about 250 m²/g, most preferably from300 m²/g to 1,000 m²/g. The support will be porous and will have a porevolume from about 0.3 to 5.0 ml/g, typically from 0.5 to 3.0 ml/g.

Silica suitable for use as a support in the present invention isamorphous. For example, some commercially available silicas are marketedunder the trademark of Sylopol® 958, 955 and 2408 by Davison Catalysts aDivision of W. R. Grace and Company and ES70 and ES70W by PQ CorporationSilica.

Treatment of the Support

The support is treated with an aqueous solution of Zr(SO₄)₂.4H₂O. Thesupport need not be dried or calcined as it is contacted with an aqueoussolution.

Generally a 2 to 50, typically a 5 to 15, preferably an 8 to 12, mostpreferably a 9 to 11 weight % aqueous solution of Zr(SO₄)₂.4H₂O is usedto treat the support. The support is contacted with the solution ofZr(SO₄)₂.4H₂O at a temperature from 10° C. to 50° C., preferably from 20to 30° C., for a time of not less than 30 minutes, typically from 1 to10 hours, preferably from 1 to 4 hours, until the support is thoroughlyimpregnated with the solution.

The impregnated support is then recovered typically by drying at anelevated temperature from 100° C. to 150° C., preferably from 120° C. to140° C., most preferably from 130° C. to 140° C., for about 8 to 12hours (e.g. overnight). Other recovery methods would be apparent tothose skilled in the art.

The dried impregnated support is then calcined. It is important that thesupport be calcined prior to the initial reaction with an aluminumactivator, catalyst or both. Generally, the support may be heated at atemperature of at least 200° C. for up to 24 hours, typically at atemperature from 500° C. to 675° C., preferably from 550° C. to 600° C.for about 2 to 20, preferably 4 to 10 hours. The resulting support willbe free of adsorbed water and should have a surface hydroxyl contentfrom about 0.1 to 5 mmol/g of support, preferably from 0.5 to 3 mmol/gof support.

The amount of the hydroxyl groups in a support may be determinedaccording to the method disclosed by J. B. Peri and A. L. Hensley, Jr.,in J. Phys. Chem., 72 (8), 2926, 1968, the entire contents of which areincorporated herein by reference.

The Zr(SO₄)₂ is substantially unchanged by calcining under theconditions noted above. At higher temperatures the Zr(SO₄)₂ starts to beconverted to ZrO.

The resulting dried and calcined support is then contacted sequentiallywith the activator and the catalyst in an inert hydrocarbon diluent.

The Activator

The activator is an aluminoxane compound of the formula R¹²₂AlO(R¹²AlO)_(q)AlR¹² ₂ wherein each R¹² is independently selected fromthe group consisting of C₁₋₂₀ hydrocarbyl radicals and q is from 3 to50. In the aluminum activator preferably R¹² is a C₁₋₄ alkyl radical,preferably a methyl radical and q is from 10 to 40. Optionally, ahindered phenol may be used in conjunction with the aluminoxane toprovide a molar ratio of Al:hindered phenol from 2:1 to 5:1 if thehindered phenol is present. Generally the molar ratio of Al:hinderedphenol, if it is present, is from 3.25:1 to 4.50:1. Preferably thephenol is substituted in the 2, 4 and 6 position by a C₂₋₆ alkylradical. Desirably the hindered phenol is2,6-di-tert-butyl-4-ethyl-phenol.

The aluminum compounds (aluminoxanes and optionally hindered phenol) aretypically used as activators in substantial molar excess compared to thetotal amount of metal in the catalysts (e.g. group 4 transition metal inthe phosphinimine catalyst). Aluminum: total metal (in the catalyst)molar ratios may range from 10:1 to 10, 000:1, preferably 10:1 to 500:1,most preferably from 50:1 to 150:1, especially from 90:1 to 120:1.

Typically the loading of the aluminoxane compound may range from 10 upto 60 weight % preferably from 15 to 50 weight %, most preferably from20 to 40 weight % based on the weight of the calcined supportimpregnated with metal salt.

The aluminoxane is added to the support in the form of a hydrocarbylsolution, typically at a 5 to 30 weight % solution, preferably an 8 to12 weight % solution, most preferably a 9 to 10 weight % solution.Suitable hydrocarbon solvents include C₅₋₁₂ hydrocarbons which may beunsubstituted or substituted by C₁₋₄ alkyl group such as pentane,hexane, heptane, octane, cyclohexane, methylcyclohexane, toluene, orhydrogenated naphtha. An additional solvent is Isopar™ E (C₈₋₁₂aliphatic solvent, Exxon Chemical Co.).

The treated support may optionally be filtered and/or dried under aninert atmosphere (e.g. N₂) and optionally at reduced pressure,preferably at temperatures from room temperature up to about 80° C.

The optionally dried support with activator is then contacted with thecatalyst again in a hydrocarbyl solution of catalyst.

In an alternate embodiment the support could be treated with a combinedsolution of activator and catalyst. However care needs to be taken withthis approach as prolonged contact (e.g. more than about 15 minutes) ofthe activator with the catalyst may result in degradation of one or bothcomponents.

The Catalyst

The catalytic component of the catalyst system is a catalyst comprisinga phosphinimine ligand and a hetero ligand, preferably bulky, of theformula:

wherein M is a group 4 metal having an atomic weight less than 179; Plis a phosphinimine ligand of the formula:

wherein each R²¹ is independently selected from the group consisting ofa hydrogen atom; a halogen atom; C₁₋₁₀ hydrocarbyl radicals which areunsubstituted by or further substituted by a halogen atom; H is aheteroligand characterized by (a) containing a heteroatom selected fromN, S, B, O, P or Si; and (b) being bonded to M through a sigma or pibond with the proviso that H is not a phosphinimine ligand as definedabove or a ketamide ligand as defined above; L is an activatable ligand;n is 1, 2 or 3 depending upon the valence of M with the proviso that Lis not a cyclopentadienyl, indenyl or fluorenyl ligand.

The preferred metals (M) are from Group 4 (especially titanium, hafniumor zirconium) with titanium being most preferred (e.g. with an atomicweight less than 179).

The phosphinimine ligand is defined by the formula:

wherein each R¹⁵ is independently selected from the group consisting ofa C₁₋₈, preferably C₁₋₆ hydrocarbyl radicals which are unsubstituted byor further substituted by a halogen atom. Most preferably thephosphinimine ligand is tris t-butyl phosphinimine.

In the catalyst preferably L is selected from the group consisting of ahydrogen atom; a halogen atom, a C₁₋₁₀ hydrocarbyl radical. Mostpreferably L is selected from the group consisting of a hydrogen atom, achlorine atom and a C₁₋₄ alkyl radical.

H is a heteroligand containing a heteroatom selected from N, S, B, O, Por Si. Some such heteroligands include silicon containing heteroligands,amido ligands, alkoxy ligands, boron heterocyclic ligands and phospholeligands. Preferred heteroligand are boron containing heteroligands.

Silicone-Containing Heteroligands

These ligands are defined by the formula:

—(μ)SiR_(x)R_(y)R_(z)

where the—denotes a bond to the transition metal and μ is sulfur oroxygen.

The substituents on the Si atom, namely R_(x), R_(y) and R_(z) arerequired in order to satisfy the bonding orbital of the Si atom. The useof any particular substituent R_(x), R_(y) or R_(z) is not especiallyimportant to the success of this invention. It is preferred that each ofR_(x), R_(y) and R_(z) is a C₁₋₄ hydrocarbyl group such as methyl,ethyl, isopropyl or tertiary butyl (simply because such materials arereadily synthesized from commercially available materials).

Amido Ligands

The term “amido” is meant to convey its broad, conventional meaning.Thus, these ligands are characterized by (a) a metal-nitrogen bond, and(b) the presence of two substituents (which are typically simple alkylor silyl groups) on the nitrogen atom.

Alkoxy Ligands

The term “alkoxy” is also intended to convey its conventional meaning.Thus these ligands are characterized by (a) a metal oxygen bond, and (b)the presence of a hydrocarbyl group bonded to the oxygen atom. Thehydrocarbyl group may be a ring structure and/or substituted (e.g. 2, 6di-tertiary butyl phenoxy).

Phosphole Ligands

The term “phosphole” is also meant to convey its conventional meaning.“Phosphole” is also meant to convey its conventional meaning.“Phospholes” are cyclic dienyl structures having four carbon atoms andone phosphorus atom in the closed ring. The simplest phosphole is C₄PH₄(which is analogous to cyclopentadiene with one carbon in the ring beingreplaced by phosphorus). The phosphole ligands may be substituted with,for example, C₁₋₂₀ hydrocarbyl radicals (which may, optionally, containhalogen substituents); phosphido radicals; amido radicals; silyl oralkoxy radicals.

Boron Heterocyclic Ligands

These ligands are characterized by the presence of a boron atom in aclosed ring ligand. This definition includes heterocyclic ligands whichalso contain a nitrogen atom in the ring. These ligands are well knownto those skilled in the art of olefin polymerization and are fullydescribed in the literature (see, for example, U.S. Pat. Nos. 5,637,659;5,554,775 and the references cited therein).

Preferred boron heterocyclic ligands have the formula:

wherein R¹⁸ is a C₁₋₄ alkyl radical.

The loading of the catalysts on the support should be such to providefrom about 0.010 to 0.50, preferably from 0.015 to 0.40, most preferablyfrom 0.015 to 0.036 mmol of metal M, preferably group 4 metal (e.g. Ti)from the catalysts per gram of support (support treated withZr(SO₄)₂.4H₂O)) and calcined and treated with an activator

The catalyst may be added to the support in a hydrocarbyl solvent suchas those noted above. The concentration of catalyst in the solvent isnot critical. Typically, it may be present in the solution in an amountfrom about 5 to 15 weight %.

The supported catalyst (e.g. support, Zr(SO₄)₂, activator and catalyst)typically has a reactivity in a dispersed phase reaction (e.g. gas orslurry phase) greater than 1,300 g of polymer per gram of support perhour normalized to an ethylene partial pressure of 200 psig (1,379 kPa)and a temperature of 90° C. in the presence of 1-hexene comonomer.

The supported catalyst of the present invention may be used in dispersedphase polymerizations in conjunction with a scavenger such as analuminum alkyl of the formula Al(R³⁰)₃ wherein R³⁰ is selected from thegroup consisting of C₁₋₁₀ alkyl radicals, preferably C₂₋₄ alkylradicals. The scavenger may be used in an amount to provide a molarratio of Al:Ti from 20 to 2,000, preferably from 50 to 1,000, mostpreferably 100 to 500. Generally the scavenger is added to the reactorprior to the catalyst and in the absence of additional poisons, overtime declines to 0.

The supported catalyst will have a kinetic profile for a plot ofethylene consumption in standard liters of ethylene per minute againsttime in minutes, corrected for the volume of ethylene in the reactorprior to the commencement of the reaction, in a 2 liter reactor over aperiod of time from 0 to 60 minutes is such that the ratio of themaximum peak height over the first 10 minutes to the average ethyleneconsumption from 10 to 60 minutes taken at not less than 40, preferablygreater than 60, most preferably from 120 to 300 data points, is lessthan 7.0, preferably less than 6, most preferably 5.5.

The supported catalyst may be used in conjunction with an antistaticagent. In one embodiment the antistatic is added directly to thesupported catalyst. The antistatic may be added in an amount from 0(e.g. optionally) up to 150,000 parts per million (ppm), preferably from15,000 up to 120,000 ppm based on the weight of the supported catalyst.

In a further embodiment the antistatic may be added to the reactor in anamount from 0 to 100, preferably from 10 to 80 ppm based on the weightof the polymer produced (i.e. the weight of polymer in the fluidized bedor the weight of polymer dispersed in the slurry phase reactor). Ifpresent the antistatic agent may be present in an amount from about 0 to100, preferably from about 10 to 80 most preferably from 20 to 50 ppmbased in the weight of polymer. From the productivity of the catalyst itis fairly routine to determine the feed rate of the antistatic to thereactor based on the catalyst feed rate.

Antistatic “Polysulfone” Additive

The antistatic polysulfone additive comprises at least one of thecomponents selected from:

-   -   (1) a polysulfone copolymer;    -   (2) a polymeric polyamine; and    -   (3) an oil-soluble sulfonic acid, and, in addition, a solvent        for the polysulfone copolymer.

Preferably, the antistatic additive comprises at least two componentsselected from above components (1), (2) and (3). More preferably, theantistatic additive comprises a mixture of (1), (2) and (3).

According to the present invention, the polysulfone copolymer componentof the antistatic additive (often designated as olefin-sulfur dioxidecopolymer, olefin polysulfones, or poly(olefin sulfone)) is a polymer,preferably a linear polymer, wherein the structure is considered to bethat of alternating copolymers of the olefins and sulfur dioxide, havinga one-to-one molar ratio of the comonomers with the olefins in head totail arrangement. Preferably, the polysulfone copolymer consistsessentially of about 50 mole percent of units of sulfur dioxide, about40 to 50 mole percent of units derived from one or more 1-alkenes eachhaving from about 6 to 24 carbon atoms, and from about 0 to 10 molepercent of units derived from an olefinic compound having the formulaACH═CHB where A is a group having the formula —(C_(x)H_(2x))—COOHwherein x is from 0 to about 17, and B is hydrogen or carboxyl, with theprovision that when B is carboxyl, x is 0, and wherein A and B togethercan be a dicarboxylic anhydride group.

Preferably, the polysulfone copolymer employed in the present inventionhas a weight average molecular weight in the range 10,000 to 1,500,000,preferably in the range 50,000 to 900,000. The units derived from theone or more 1-alkenes are preferably derived from straight chain alkeneshaving 6-18 carbon atoms, for example 1-hexene, 1-heptene, 1-octene,1-decene, 1-dodecene, 1-hexadecene and 1-octadecene. Examples of unitsderived from the one or more compounds having the formula ACH═CHB areunits derived from maleic acid, acrylic acid, 5-hexenoic acid.

A preferred polysulfone copolymer is 1-decene polysulfone having aninherent viscosity (measured as a 0.5 weight percent solution in tolueneat 30° C.) ranging from about 0.04 dl/g to 1.6 dl/g.

The polymeric polyamines that can be suitably employed in the antistaticof the present invention are described in U.S. Pat. No. 3,917,466, inparticular at column 6 line 42 to column 9 line 29.

The polyamine component in accordance with the present invention has thegeneral formula:

R²⁰N[(CH₂CHOHCH₂NR²¹)_(a)—(CH₂CHOHCH₂NR²¹—R²²—NH)_(b)—(CH₂CHOHCH₂NR²³)_(c)H_(x)]H_(2-x)

wherein R²¹ is an aliphatic hydrocarbyl group of 8 to 24 carbon atoms;R²² is an alkylene group of 2 to 6 carbon atoms; R²³ is the groupR²²—HNR²¹; R²⁰ is R²¹ or an N-aliphatic hydrocarbyl alkylene grouphaving the formula R²¹NHR²²; a, b and c are integers from 0 to 20 and xis 1 or 2; with the proviso that when R²⁰ is R²¹ then a is greater than2 and b=c=0, and when R²⁰ is R²¹NHR²² then a is 0 and the sum of b+c isan integer from 2 to 20.

The polymeric polyamine may be prepared for example by heating analiphatic primary monoamine or N-aliphatic hydrocarbyl alkylene diaminewith epichlorohydrin in the molar proportion of from 1:1 to 1:1.5 at atemperature of 50° C. to 100° C. in the presence of a solvent, (e.g. amixture of xylene and isopropanol) adding a strong base, (e.g. sodiumhydroxide) and continuing the heating at 50 to 100° C. for about 2hours. The product containing the polymeric polyamine may then beseparated by decanting and then flashing off the solvent.

The polymeric polyamine is preferably the product of reacting anN-aliphatic hydrocarbyl alkylene diamine or an aliphatic primary aminecontaining at least 8 carbon atoms and preferably at least 12 carbonatoms with epichlorohydrin. Examples of such aliphatic primary aminesare those derived from tall oil, tallow, soy bean oil, coconut oil andcotton seed oil. The polymeric polyamine derived from the reaction oftallowamine with epichlorohydrin is preferred. A method of preparingsuch a polyamine is disclosed in U.S. Pat. No. 3,917,466, column 12,preparation B.1.0

The above-described reactions of epichlorohydrin with amines to formpolymeric products are well known and find extensive use in epoxideresin technology.

A preferred polymeric polyamine is a 1:1.5 mole ratio reaction productof N-tallow-1,3-diaminopropane with epichlorohydrin. One such reactionproduct is “Polyflo™ 130” sold by Universal Oil Company.

According to the present invention, the oil-soluble sulfonic acidcomponent of the antistatic is preferably any oil-soluble sulfonic acidsuch as an alkanesulfonic acid or an alkylarylsulfonic acid. A usefulsulfonic acid is petroleum sulfonic acid resulting from treating oilswith sulfuric acid.

Preferred oil-soluble sulfonic acids are dodecylbenzenesulfonic acid anddinonylnaphthylsulfonic acid.

The antistatic additive preferably comprises 1 to 25 weight % of thepolysulfone copolymer, 1 to 25 weight % of the polymeric polyamine, 1 to25 weight % of the oil-soluble sulfonic acid and 25 to 95 weight % of asolvent. Neglecting the solvent, the antistatic additive preferablycomprises about 5 to 70 weight % polysulfone copolymer, 5 to 70 weight %polymeric polyamine and 5 to 70 weight % oil-soluble sulfonic acid andthe total of these three components is preferably 100%.

Suitable solvents include aromatic, paraffin and cycloparaffincompounds. The solvents are preferably selected from among benzene,toluene, xylene, cyclohexane, fuel oil, isobutane, kerosene and mixturesthereof.

According to a preferred embodiment of the present invention, the totalweight of components (1), (2), (3) and the solvent representsessentially 100% of the weight of the antistatic additive.

One useful composition, for example, consists of 13.3 weight % 1:1copolymer of 1-decene and sulfur dioxide having an inherent viscosity of0.05 determined as above, 13.3 weight % of “Polyflo™ 130” (1:1.5 moleratio reaction product of N-tallow-1,3-diaminopropane withepichlorohydrin), 7.4 weight % of either dodecylbenzylsulfonic acid ordinonylnaphthylsulfonic acid, and 66 weight % of an aromatic solventwhich is preferably toluene or kerosene.

Another useful composition, for example, consists of 2 to 7 weight % 1:1copolymer of 1-decene and sulfur dioxide having an inherent viscosity of0.05 determined as above, 2 to 7 weight % of “Palyflo™ 130” (1:1.5 moleratio reaction product of N-tallow-1,3-diaminopropane withepichlorohydrin), 2 to 8 weight % of either dodecylbenzylsulfonic acidor dinonylnaphthylsulfonic acid, and 78 to 94 weight % of an aromaticsolvent which is preferably a mixture of 10 to 20 weight % toluene and62 to 77 weight % kerosene.

According to a preferred embodiment of the present invention, theantistatic is a material sold by Octel under the trade name STADIS™,preferably STADIS 450, more preferably STADIS 425.

Gas Phase Polymerization

Fluidized bed gas phase reactors to make polyethylene are generallyoperated at low temperatures from about 50° C. up to about 120° C.(provided the sticking temperature of the polymer is not exceeded)preferably from about 75° C. to about 110° C. and at pressures typicallynot exceeding 3,447 kPa (about 500 psi) preferably not greater thanabout 2,414 kPa (about 350 psi).

Gas phase polymerization of olefins is well known. Typically, in the gasphase polymerization of olefins (such as ethylene) a gaseous feed streamcomprising of at least about 80 weight % ethylene and the balance one ormore C₃₋₆ copolymerizable monomers typically, 1-butene, or 1-hexene orboth, together with a ballast gas such as nitrogen, optionally a smallamount of C₁₋₂ alkanes (i.e. methane and ethane) and further optionallya molecular weight control agent (typically hydrogen) is fed to areactor and in some cases a condensable hydrocarbon (e.g. a C₄₋₆ alkanesuch as pentane). Typically, the feed stream passes through adistributor plate at the bottom of the reactor and vertically traversesa bed of polymer particles with active catalyst, typically a fluidizedbed but the present invention also contemplates a stirred bed reactor. Asmall proportion of the olefin monomers in the feed stream react withthe catalyst. The unreacted monomer and the other non-polymerizablecomponents in the feed stream exit the bed and typically enter adisengagement zone where the velocity of the feed stream is reduced sothat entrained polymer falls back into the fluidized bed. Typically thegaseous stream leaving the top of the reactor is then passed through acompressor. The compressed gas is then cooled by passage through a heatexchanger to remove the heat of reaction. The heat exchanger may beoperated at temperatures below about 65° C., preferably at temperaturesfrom 20° C. to 50° C. If there is a condensable gas it is usuallycondensed and entrained in the recycle stream to remove heat of reactionby vaporization as it recycles through the fluidized bed.

Polymer is removed from the reactor through a series of vessels in whichmonomer is separated from the off gases. The polymer is recovered andfurther processed. The off gases are fed to a monomer recovery unit. Themonomer recovery unit may be selected from those known in the artincluding a distillation tower (i.e. a C₂ splitter), a pressure swingadsorption unit and a membrane separation device. Ethylene and hydrogengas recovered from the monomer recovery unit are fed back to thereactor. Finally, make up feed stream is added to the reactor below thedistributor plate.

Slurry Polymerization

Slurry processes are conducted in the presence of a hydrocarbon diluentsuch as an alkane (including isoalkanes), an aromatic or a cycloalkane.The diluent may also be the alpha olefin comonomer used incopolymerizations. Preferred alkane diluents include propane, butanes,(i.e. normal butane and/or isobutane), pentanes, hexanes, heptanes andoctanes. The monomers may be soluble in (or miscible with) the diluent,but the polymer is not (under polymerization conditions). Thepolymerization temperature is preferably from about 5° C. to about 200°C., most preferably less than about 110° C. typically from about 10° C.to 80° C. The reaction temperature is selected so that the ethylenecopolymer is produced in the form of solid particles. The reactionpressure is influenced by the choice of diluent and reactiontemperature. For example, pressures may range from 15 to 45 atmospheres(about 220 to 660 psi or about 1,500 to about 4,600 kPa) when isobutaneis used as diluent (see, for example, U.S. Pat. No. 4,325,849) toapproximately twice that (i.e. from 30 to 90 atmospheres—about 440 to1,300 psi or about 3,000-9,100 kPa) when propane is used (see U.S. Pat.No. 5,684,097). The pressure in a slurry process must be keptsufficiently high to keep at least part of the ethylene monomer in theliquid phase.

The reaction typically takes place in a jacketed closed loop reactorhaving an internal stirrer (e.g. an impeller) and at least one settlingleg. Catalyst, monomers and diluents are fed to the reactor as liquidsor suspensions. The slurry circulates through the reactor and the jacketis used to control the temperature of the reactor. Through a series oflet down valves the slurry enters a settling leg and then is let down inpressure to flash the diluent and unreacted monomers and recover thepolymer generally in a cyclone. The diluent and unreacted monomers arerecovered and recycled back to the reactor.

The slurry reaction may also be conducted in a continuous stirred tankreactor.

The Polymer

The resulting polymer may have a density from about 0.910 g/cc to about0.960 g/cc. The resulting polymers may be used in a number ofapplications such as blown and cast film, extrusion and both injectionand rotomolding applications. Typically the polymer may be compoundedwith the usual additives including heat and light stabilizers such ashindered phenols; ultra violet light stabilizers such as hindered aminestabilizers (HALS); process aids such as fatty acids or theirderivatives and fluoropolymers optionally in conjunction with lowmolecular weight esters of polyethylene glycol.

The present invention will now be illustrated by the following nonlimiting example.

Catalyst

The Borabenzene complex was prepared following the literaturepreparation found in Herberich, G. E.; Schmidt, B.; Englert, U.Organometallics, 1995, 14, 471-480. The titanium precursor complex wasprepared using the preparation found in U.S. Pat. No. 6,147,172 issuedNov. 14, 2000 to Brown et al., assigned to NOVA Chemicals InternationalS.A.

Complexation

The final catalyst molecule was prepared by adding an ethereal solution(20 mL) of the borabenzene salt (0.2 g, 2.1 mmol) to a solution of thetitanium precursor (0.8 g, 2.1 mmol) dissolved in ether (25 mL) at −90°C. The resultant yellow solution was stirred overnight and graduallywarm to room temperature. Ether was removed in vacuo and the product wasextracted into dichloromethane (2×10 mL) and volatiles were removedagain. The crude product was extracted into toluene (2×10 mL) andlayered with heptane to crystallize a solid product which was isolatedby filtration (0.6 g, 68%).

The aluminoxane was a 10% MAO solution in toluene supplied by Albemarle.

The support was silica SYLOPOL 2408 obtained from W.R. Grace.

Preparation of the Support (Apart from the Control)

A 10% aqueous solution of the Zr(SO₄).4H₂O was prepared and impregnatedinto the support by incipient wetness impregnation procedure. The solidsupport was dried in air at about 135° C. to produce a free flowingpowder. The resulting powder was subsequently dried in air at 200° C.for about 2 hours under air and then under nitrogen at 600° C. for 6hours.

NAA Characterization

A sample of Zr(SO₄)₂ treated SYLOPOL 2408 prepared as above wasdetermined to have a sulfur:zirconium ratio of 0.703 by NAA analysis;which is consistent with the ratio expected for pure Zr(SO₄)₂.

XRD Analysis

A 1 gram sample of pure Zr(SO₄)₂.4H₂O was dehydrated in a muffle furnaceat 600° C. for 6 hours and the solid was analyzed by XRD analysis, whichshowed 100% of the Zr(SO₄)₂ remained.

The above shows that zirconia is not formed by the calcination processof Zr(SO₄)₂.4H₂O at up to 600° C. under nitrogen.

To a slurry of calcined support in toluene was added a toluene solutionof 10 weight % MAO (4.5 weight % Al, purchased from Albemarle) plusrinsings (3×5 mL). The resultant slurry was mixed using a shaker for 1hour at ambient temperature. To this slurry of MAO-on-support was addeda toluene solution of catalyst to give a molar ratio of Al:Ti of 120:1.After two hours of mixing at room temperature using a shaker, the slurrywas filtered, yielding a colorless filtrate. The solid component waswashed with toluene and pentane (2×), then separated ˜400 mTorr andsealed under nitrogen until use.

For the comparative example the same procedure was used except that thesupport was not treated with Zr(SO₄).4H₂O.

Polymerization

A 2 L reactor fitted with a stirrer (˜675 rpm) containing a NaCl seedbed (160 g) (stored for at least 3 days at 130° C.) was conditioned for30 minutes at 105° C. An injection tube loaded in the gloveboxcontaining the catalyst formulation was inserted into the reactorsystem, which was then purged 3 times with nitrogen and once withethylene at 200 psi. Pressure and temperature were reduced in thereactor (below 2 psi and between 60 and 85° C.) and TIBAL (500:1 Al:Ti)was injected via gastight syringe followed by a 2 mL precharge of1-hexene. After the reactor reached 85° C. the catalyst was injected viaethylene pressure and the reactor was pressurized to 200 psi totalpressure with 1-hexene fed with a syringe pump at a mole ratio of 6.5%C₆/C₂ started 1 minute after catalyst injection. The temperature ofreaction was controlled at 90° C. for a total runtime of 60 minutes.Reaction was halted by stopping the ethylene flow and turning on reactorcooling water. The reactor was vented slowly to minimize loss ofcontents and the polymer/salt mixture was removed and allowed to air drybefore being weighed.

Fouling was measured by collecting the polymer from the reactor(including lumps and sheeted material) and sieving through a number 14sieve (1.4 mm openings) the product (lightly brushing but not “pushing”product through) to determine what percent of the polymer did not passthrough the sieve as a percent of the total polymer produced. Theresults of the experiments are set forth in Table 1 below.

TABLE 1 Time AL:Ti Productivity Max to Rate of Max height 1-10/ MolargPE/g C₂ Max Rise Average C₂ Support ratio catalyst Flow Flow scLM/minconcentration Fouling % Catalyst 120:1 1333 2.75 1.50 1.83 5.47 58.9Zr(SO₄)₂/2408. Catalyst 120:1 1500 3.82 1.94 1.96 7.47 66.7 2408

FIG. 1 is a kinetic profile of the catalyst on silica and modifiedsilica. As noted above the catalyst is extremely “hot” and bothcatalysts have a very significant initial rate of reaction. However,after about a minute it is clear the modified catalyst has a lower andmore consistent rate of reaction.

1. A catalyst system having an activity greater than 1,300 g of polymerper gram of supported catalyst per hour normalized to 1,379 kPag (200psig) of ethylene partial pressure and a temperature of 90° C. in thepresence of 1-hexene comonomer and a kinetic profile for a plot ofethylene consumption in standard liters of ethylene per minute againsttime in minutes, at a reaction pressure of 1,379 kPag (200 psig) and 90°C., corrected for the volume of ethylene in the reactor prior to thecommencement of the reaction, in a 2 liter reactor over a period of timefrom 0 to 60 minutes is such that the ratio of the maximum peak heightover the first 10 minutes to the average ethylene consumption from 10 to60 minutes taken at not less than 40 data points, is less than 6,comprising: (i) an inorganic oxide support having an average particlesize from 10 to 150 microns, a surface area greater than 100 m²/g, and apore volume greater than 0.3 ml/g impregnated with (ii) at least a 1weight % based on the weight of alumina of Zr(SO₄)₂.4H₂O, based on theweight of the support of said salt; (iii) from 10 to 60 weight % of analuminum activator based on the weight of said alumina support saidactivator having the formula:R¹² ₂AlO(R¹²AlO)_(q)AlR¹² ₂  wherein each R¹² is independently selectedfrom the group consisting of C₁₋₂₀ hydrocarbyl radicals and q is from 3to 50; and (iv) from 0.1 to 30 weight % of a catalyst of the formula:

 wherein M is a group 4 metal having an atomic weight less than 179; Plis a phosphinimine ligand of the formula

 wherein each R²¹ is independently selected from the group consisting ofa hydrogen atom; a halogen atom; C₁₋₁₀ hydrocarbyl radicals which areunsubstituted by or further substituted by a halogen atom; H is aheteroligand characterized by (a) containing a heteroatom selected fromN, S, B, O or P; and (b) being bonded to M through a sigma or pi bondwith the proviso that H is not a phosphinimine ligand as defined aboveor a ketamide ligand L is an activatable ligand; n is 1, 2 or 3depending upon the valence of M with the proviso that L is not acyclopentadienyl, indenyl or fluorenyl ligand.
 2. The catalyst accordingto claim 1, wherein H is a boron heteroligand of the formula

wherein R¹⁸ is a C₁₋₄ alkyl radical.
 3. The catalyst according to claim2, further comprising from 50 to 250 ppm based on the weight of thesupported catalyst of an antistatic comprising: (i) from 3 to 48 partsby weight of one or more polysulfones comprising: (a) 50 mole % ofsulphur dioxide; (b) 40 to 50 mole % of a C₆₋₂₀ an alpha olefin; and (c)from 0 to 10 mole % of a compound of the formula ACH═CHB where A isselected from the group consisting of a carboxyl radical and a C₁₋₁₅carboxy alkyl radical and B is a hydrogen atom or a carboxyl radicalprovided if A and B are carboxyl radicals A and B may form an anhydride;(ii) from 3 to 48 parts by weight of one or more polymeric polyamides ofthe formula:R²⁰N[(CH₂CHOHCH₂NR²¹)_(a)—(CH₂CHOHCH₂NR²¹—R²²—NH)_(b)—(CH₂CHOHCH₂NR²³)_(c)H_(x)]H_(2-x) wherein R²¹ is an aliphatic hydrocarbyl group of 8 to 24 carbon atoms;R²² is an alkylene group of 2 to 6 carbon atoms; R²³ is the groupR²²—HNR²¹; R²⁰ is R²¹ or an N-aliphatic hydrocarbyl alkylene grouphaving the formula R²¹NHR²²; a, b and c are integers from 0 to 20 and xis 1 or 2; with the proviso that when R²⁰ is R²¹ then a is greater than2 and b=c=0, and when R²⁰ is R²¹NHR²² then a is 0 and the sum of b+c isan integer from 2 to 20; and (iii) from 3 to 48 parts by weight ofC₁₀₋₂₀ alkyl or arylalkyl sulphonic acid.
 4. A process of making acatalyst system having an activity greater than 1,300 g of polymer pergram of supported catalyst per hour normalized to 1,379 kPag (200 psig)of ethylene partial pressure and a temperature of 90° C. in the presenceof 1-hexene comonomer and a kinetic profile for a plot of ethyleneconsumption in standard liters of ethylene per minute against time inminutes, at a reaction pressure of 1,379 kPag (200 psig) and 90° C.,corrected for the volume of ethylene in the reactor prior to thecommencement of the reaction, in a 2 liter reactor over a period of timefrom 0 to 60 minutes is such that the ratio of the maximum peak heightover the first 10 minutes to the average ethylene consumption from 10 to60 minutes taken at not less than 40 data points, is less than 6,comprising: (i) impregnating a silica support having an average particlesize from 10 to 150 microns, a surface area greater than 100 m²/g, and apore volume greater than 0.3 ml/g with (ii) an aqueous solution ofZr(SO₄)₂.4H₂O, to provide not less than 1 weight % based on the weightof the support; (iii) recovering the impregnated support; (iv) calciningsaid impregnated support in one or more steps at a temperature from 300°C. to 600° C. for a time from 2 to 20 hours in an inert atmosphere; (v)and either (a) contacting said calcined support with a hydrocarbylsolution of an aluminum activator compound of the formula:R¹² ₂AlO(R¹²AlO)_(q)AlR¹² ₂  wherein each R¹² is independently selectedfrom the group consisting of C₁₋₂₀ hydrocarbyl radicals and q is from 3to 50 to provide from 10 to 60 weight % of said aluminum compound basedon the weight of said calcined support; optionally, separating saidactivated support from said hydrocarbyl solution and contacting saidactivated support with a hydrocarbyl solution of a single site catalystas set out below to provide from 0.1 to 30 weight % of said catalyst; or(b) contacting said support with a hydrocarbyl solution of an aluminumactivator compound of the formula:R¹² ₂AlO(R¹²AlO)_(q)AlR¹² ₂  wherein each R¹² is independently selectedfrom the group consisting of C₁₋₂₀ hydrocarbyl radicals and q is from 3to 50 to provide from 10 to 60 weight % of said aluminum compound basedon the weight of said calcined support; and a single site catalyst ofthe formula:

 wherein M is a group 4 metal having an atomic weight less than 179; Plis a phosphinimine ligand of the formula

 wherein each R²¹ is independently selected from the group consisting ofa hydrogen atom; a halogen atom; C₁₋₁₀ hydrocarbyl radicals which areunsubstituted by or further substituted by a halogen atom; H is aheteroligand characterized by (a) containing a heteroatom selected fromN, S, B, O, P, or Si; and (b) being bonded to M through a sigma or pibond with the proviso that H is not a phosphinimine ligand as definedabove or a ketamide ligand L is an activatable ligand; n is 1, 2 or 3depending upon the valence of M with the proviso that L is not acyclopentadienyl, indenyl or fluorenyl ligand to provide form 0.1 to 30weight % of said catalyst; and (vi) recovering and drying the catalyst.5. The catalyst according to claim 4, wherein H is a boron heteroligandof the formula

wherein R¹⁸ is a C₁₋₄ alkyl radical.
 6. The process according to claim5, further comprising contacting said catalyst with from 15,000 to120,000 ppm based on the weight of the supported catalyst of anantistatic comprising: (i) from 3 to 48 parts by weight of one or morepolysulfones comprising: (a) 50 mole % of sulphur dioxide; (b) 40 to 50mole % of a C₆₋₂₀ an alpha olefin; and (c) from 0 to 10 mole % of acompound of the formula ACH═CHB where A is selected from the groupconsisting of a carboxyl radical and a C₁₋₁₅ carboxy alkyl radical; andB is a hydrogen atom or a carboxyl radical provided if A and B arecarboxyl radicals A and B may form an anhydride; (ii) from 3 to 48 partsby weight of one or more polymeric polyamides of the formula:RN[(CH₂CHOHCH₂NR¹)_(a)—(CH₂CHOHCH₂NR¹—R²—NH)_(b)—(CH₂CHOHCH₂NR³)_(c)H]H_(2-x) wherein R¹ is an aliphatic hydrocarbyl group of 8 to 24 carbon atoms;R² is an alkylene group of 2 to 6 carbon atoms; R³ is the group-R²—HNR¹;R is R¹ or an N-aliphatic hydrocarbyl alkylene group having the formulaR¹NHR²; a, b and c are integers from 0 to 20 and x is 1 or 2; with theproviso that when R is R¹ then a is greater than 2 and b=c=0, and when Ris R¹NHR² then a is 0 and the sum of b+c is an integer from 2 to 20; and(iii) from 3 to 48 parts by weight of C₁₀₋₂₀ alkyl or arylalkylsulphonic acid and optionally from 0 to 150 parts by weight of a solventor diluent.
 7. A dispersed phase olefin polymerization process havingimproved reactor continuity conducted in the presence of a catalystprepared according to claim
 2. 8. A disperse phase polymerizationprocess comprising contacting one or more C₂₋₈ alpha olefins with acatalyst system according to claim 1, and feeding to the reactor from 10to 80 ppm based on the weight of the polymer produced of an antistaticcomprising: (i) from 3 to 48 parts by weight of one or more polysulfonescomprising: (a) 50 mole % of sulphur dioxide; (b) 40 to 50 mole % of aC₆₋₂₀ an alpha olefin; and (c) from 0 to 10 mole % of a compound of theformula ACH═CHB where A is selected from the group consisting of acarboxyl radical and a C₁₋₁₅ carboxy alkyl radical and B is a hydrogenatom or a carboxyl radical provided if A and B are carboxyl radicals Aand B may form an anhydride; (ii) from 3 to 48 parts by weight of one ormore polymeric polyamides of the formula:R²⁰N[(CH₂CHOHCH₂NR²¹)_(a)—(CH₂CHOHCH₂NR²¹—R²²—NH)_(b)—(CH₂CHOHCH₂NR²³)_(c)H_(x)]H_(2-x) wherein R²¹ is an aliphatic hydrocarbyl group of 8 to 24 carbon atoms;R²² is an alkylene group of 2 to 6 carbon atoms; R²³ is the groupR²²—HNR²¹; R²⁰ is R²¹ or an N-aliphatic hydrocarbyl alkylene grouphaving the formula R²¹NHR²²; a, b and c are integers from 0 to 20 and xis 1 or 2; with the proviso that when R²⁰ is R²¹ then a is greater than2 and b=c=0, and when R²⁰ is R²¹NHR²² then a is 0 and the sum of b+c isan integer from 2 to 20; and (iii) from 3 to 48 parts by weight ofC₁₀₋₂₀ alkyl or arylalkyl sulphonic acid.